Catalyst composition comprising ruthenium and zirconium and processes therefor and therewith for preparing high molecular weight hydrocarbons such as polymethylene

Abstract

A catalyst composition and a process of using a catalyst composition for preparing high molecular weight hydrocarbons, such as polymethylene, from a fluid containing hydrogen and carbon monoxide are disclosed. The catalyst composition contains ruthenium and zirconium. The zirconium can be present as a zirconium component that can be selected from zirconyl phosphate, zirconium oxide, and zirconium phosphate prepared by processes of the present invention.

1. A process of preparing a high molecular weight hydrocarbon comprising contacting, under reaction conditions, a catalyst composition and a fluid comprising hydrogen and carbon monoxide wherein said catalyst composition is prepared by a process comprising contacting a ruthenium component and a zirconium component wherein said contacting of said catalyst composition and said fluid is conducted in the presence of a solvent selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane, and combinations thereof, and wherein said contacting said ruthenium component and said zirconium component comprises vapor phase deposition, contacting under a pressure drying condition, and combinations thereof. 
     
     
       2. A process according to  claim 1  wherein said high molecular weight hydrocarbon comprises a molecular weight greater than about 2×10 3  molecular weight units. 
     
     
       3. A process according to  claim 1  wherein said high molecular weight hydrocarbon comprises polymethylene. 
     
     
       4. A process according to  claim 1  wherein a mole ratio of said hydrogen to said carbon monoxide is in the range of from about 1:1 to about 5:1. 
     
     
       5. A process according to  claim 1  wherein said reaction conditions comprise:
 a temperature in the range of from about 100° C. to about 500° C.,  
 a pressure in the range of from about 500 pounds per square inch gauge to about 10,000 pounds per square inch gauge, and  
 a charge rate of said fluid such that the weight hourly space velocity is in the range of from about 0.01 hours −1  to about 1000 hour −1 .  
 
     
     
       6. A process according to  claim 1  wherein a weight ratio of said solvent to catalyst composition is in the range of from about 400:1 to about 20:1. 
     
     
       7. A process according to  claim 1  wherein said process of preparing a high molecular weight hydrocarbon is conducted in a slurry phase reactor. 
     
     
       8. A process according to  claim 1  wherein said ruthenium component is selected from the group consisting of ruthenium bromide, ruthenium bromide hydrate, ruthenium chloride, ruthenium chloride hydrate, ruthenium iodide, ruthenium nitrosyl nitrate, ruthenium oxide, ruthenium oxide hydrate, ruthenium tetraoxide, and combinations thereof. 
     
     
       9. A process according to  claim 1  wherein said ruthenium component comprises ruthenium chloride, ruthenium nitrosyl nitrate, or ruthenium oxide. 
     
     
       10. A process according to  claim 1  wherein said zirconium component is selected from the group consisting of zirconium oxide, zirconium phosphate, zirconyl phosphate, and combinations thereof. 
     
     
       11. A process according to  claim 1  wherein said pressure drying condition comprises:
 a temperature in the range of from about 200° C. to about 500° C.,  
 a pressure in the range of from about 14.7 pounds per square inch absolute to about 400 pounds per square inch absolute,  
 a time period of from about 0.5 hour to about 10 hours, and  
 further wherein said pressure drying condition comprises an atmosphere selected from the group consisting of nitrogen, argon, and combinations thereof.  
 
     
     
       12. A process according to  claim 1  wherein an amount of said ruthenium component is such as to provide a concentration of ruthenium in said catalyst composition in the range of from about 1 weight percent to about 30 weight percent based on the total weight of said catalyst composition. 
     
     
       13. A process according to  claim 1  wherein an amount of said zirconium component is such as to provide a concentration of zirconium in said catalyst composition in the range of from about 10 weight percent to about 90 weight percent based on the total weight of said catalyst composition. 
     
     
       14. A process according to  claim 1  further comprises, after contacting said zirconium component and said ruthenium component, treating under a treating condition comprising:
 a temperature in the range of from about 250° C. to about 1000° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 750 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 30 hours, and  
 further wherein said treating condition comprises an atmosphere selected from the group consisting of an oxygen-containing atmosphere, nitrogen, argon, and combinations thereof.  
 
     
     
       15. A process according to  claim 1  wherein said process further comprises, after contacting said zirconium component and said ruthenium component, activating under an activating condition comprising:
 a temperature in the range of from about 50° C. to about 500° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 750 pounds per square inch absolute,  
 a time period in the range of from about 0.1 hour to about 30 hours, and  
 further wherein said activating condition comprises an atmosphere selected from the group consisting of hydrogen, carbon monoxide, synthesis gas, other reducing gases, and combinations thereof.  
 
     
     
       16. A process according to  claim 15  further comprises, after said activating, contacting with an ammonia component selected from the group consisting of ammonium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, and combinations thereof followed by reactivating by subjecting to activating under said activating condition. 
     
     
       17. A process according to  claim 14  further comprises, after said contacting said zirconium component and said ruthenium component and before said treating under a treating condition, drying under a drying condition comprising:
 a temperature in the range of from about 20° C. to about 200° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 200 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 10 hours, and  
 further wherein said drying condition comprises an atmosphere comprising air.  
 
     
     
       18. A process according to  claim 1  wherein a weight ratio of zirconium to ruthenium of said catalyst composition is in the range of from about 0.01:1 to about 5:1. 
     
     
       19. A process according to  claim 10  wherein said zirconyl phosphate is prepared by a process comprising contacting a zirconyl salt and a water-soluble acidic phosphorous compound. 
     
     
       20. A process according to  claim 19  wherein said water-soluble acidic phosphorous compound is selected from the group consisting of phosphoric acid, phosphorous acid, and combinations thereof. 
     
     
       21. A process according to  claim 19  wherein said water-soluble acidic phosphorous compound is phosphoric acid. 
     
     
       22. A process according to  claim 19  wherein a weight ratio of said zirconyl salt to said water-soluble acidic phosphorous compound is in the range of from about 0.5:1 to about 10:1. 
     
     
       23. A process according to  claim 19  wherein said process of preparing said zirconyl phosphate further comprises contacting said zirconyl salt and water-soluble acidic phosphorous compound with a hydroxide component under a precipitating condition to provide for an increase of pH and for precipitating said zirconyl phosphate. 
     
     
       24. A process according to  claim 23  wherein said precipitating condition comprises:
 a temperature in the range of from about 20° C. to about 90° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 100 pounds per square inch absolute, and  
 a time period in the range of from about 0.1 hour to about 10 hours.  
 
     
     
       25. A process according to  claim 19  wherein said zirconyl salt is selected from the group consisting of zirconyl chloride hydrate, zirconyl chloride octahydrate, zirconyl nitrate hydrate, zirconyl nitrate, zirconyl perchlorate octahydrate, and combinations thereof. 
     
     
       26. A process according to  claim 19  wherein said zirconyl salt comprises zirconyl nitrate hydrate. 
     
     
       27. A process according to  claim 23  wherein said hydroxide component is selected from the group consisting of ammonium hydroxide, tetramethyl ammonium hydroxide, tetramethyl ammonium bromide, tetraethyl ammonium bromide, lithium hydroxide, sodium hydroxide, sodium hydrosulfide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, sodium carbonate, sodium oxide, sodium sulfate, magnesium oxide, calcium oxide, calcium carbonate, sodium phenoxide, barium phenoxide, calcium phenoxide, and combinations thereof. 
     
     
       28. A process according to  claim 27  wherein said hydroxide component comprises ammonium hydroxide. 
     
     
       29. A process according to  claim 23  wherein a weight ratio of said hydroxide component to said zirconyl salt and water-soluble acidic phosphorous compound is in the range of from about 0.01:1 to about 1:1. 
     
     
       30. A process according to  claim 19  wherein said process of preparing said zirconyl phosphate further comprises contacting said zirconyl phosphate with an aqueous solution. 
     
     
       31. A process according to  claim 19  wherein said process of preparing said zirconyl phosphate further comprises contacting with an alcohol selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and combinations thereof. 
     
     
       32. A process according to  claim 19  wherein said process of preparing said zirconyl phosphate further comprises drying under a drying condition comprising:
 a temperature in the range of from about 20° C. to about 200° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 200 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 10 hours, and  
 further wherein said drying condition comprises an atmosphere comprising air.  
 
     
     
       33. A process according to  claim 19  wherein said process of preparing said zirconyl phosphate further comprises calcining under a calcining condition comprising:
 a temperature in the range of from about 250° C. to about 1000° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 750 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 30 hours, and  
 further wherein said calcining condition comprises an atmosphere comprising air.  
 
     
     
       34. A process according to  claim 23  wherein said process of preparing said zirconyl phosphate further comprises contacting said zirconyl phosphate with a silica component selected from the group consisting of silica, colloidal silica, silica gel, and combinations thereof. 
     
     
       35. A process according to  claim 34  wherein said silica component is silica gel. 
     
     
       36. A process according to  claim 34  wherein said contacting said zirconyl phosphate with a silica component occurs during said precipitating of said zirconyl phosphate. 
     
     
       37. A process according to  claim 34  wherein a weight ratio of said silica component to said zirconyl phosphate is in the range of from about 0.01:1 to about 1:1. 
     
     
       38. A process according to  claim 10  wherein a process of preparing said zirconium oxide comprises contacting a zirconyl salt and an ammonia component under a precipitating condition. 
     
     
       39. A process according to  claim 38  wherein said precipitating condition comprises:
 a temperature in the range of from about 20° C. to about 90° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 100 pounds per square inch absolute, and  
 a time period in the range of from about 0.1 hour to about 10 hours.  
 
     
     
       40. A process according to  claim 38  wherein a weight ratio of said zirconyl salt to said ammonia component is in a range of from about 0.5:1 to about 10:1. 
     
     
       41. A process according to  claim 38  wherein said zirconyl salt is selected from the group consisting of zirconyl chloride hydrate, zirconyl chloride octahydrate, zirconyl nitrate hydrate, zirconyl nitrate, zirconyl perchlorate octahydrate, and combinations thereof. 
     
     
       42. A process according to  claim 38  wherein said zirconyl salt comprises zirconyl nitrate hydrate. 
     
     
       43. A process according to  claim 38  wherein said ammonia component is selected from the group consisting of ammonia, ammonium acetate, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium fluoride, ammonium iodide, ammonium nitrate, ammonium sulfate, and combinations thereof. 
     
     
       44. A process according to  claim 38  wherein said process of preparing said zirconium oxide further comprises contacting said zirconium oxide with an aqueous solution. 
     
     
       45. A process according to  claim 38  wherein said process of preparing said zirconium oxide further comprises contacting with an alcohol selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and combinations thereof. 
     
     
       46. A process according to  claim 38  wherein said process of preparing said zirconium oxide further comprises pressure drying under a pressure drying condition comprising:
 a temperature in the range of from about 200° C. to about 500° C.,  
 a pressure in the range of from about 14.7 pounds per square inch absolute to about 400 pounds per square inch absolute,  
 a time period of from about 0.5 hour to about 10 hours, and  
 further wherein said pressure drying condition comprises an atmosphere selected from the group consisting of nitrogen, argon, and combinations thereof.  
 
     
     
       47. A process according to  claim 38  wherein said process of preparing said zirconium oxide further comprises drying under a drying condition comprising:
 a temperature in the range of from about 20° C. to about 200° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 200 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 10 hours, and  
 further wherein said drying condition comprises an atmosphere comprising air.  
 
     
     
       48. A process according to  claim 38  wherein said process of preparing said zirconium oxide further comprises calcining under a calcining condition comprising:
 a temperature in the range of from about 250° C. to about 1000° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 750 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 30 hours, and  
 further wherein said calcining condition comprises an atmosphere comprising air.  
 
     
     
       49. A process according to  claim 10  wherein a process of preparing said zirconium phosphate comprises contacting a zirconyl salt and a water-soluble acidic phosphorous compound under a precipitating condition. 
     
     
       50. A process according to  claim 49  wherein said water-soluble acidic phosphorous compound is selected from the group consisting of phosphoric acid, phosphorous acid, and combinations thereof. 
     
     
       51. A process according to  claim 49  wherein said water-soluble acidic phosphorous compound is phosphoric acid. 
     
     
       52. A process according to  claim 49  wherein a weight ratio of said zirconyl salt to said water-soluble acidic phosphorous compound is in a range of from about 0.5:1 to about 10:1. 
     
     
       53. A process according to  claim 49  wherein said precipitating condition comprises:
 a temperature in the range of from about 20° C. to about 90° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 100 pounds per square inch absolute, and  
 a time period in the range of from about 0.1 hour to about 10 hours.  
 
     
     
       54. A process according to  claim 49  wherein said zirconyl salt is selected from the group consisting of zirconyl chloride hydrate, zirconyl chloride octahydrate, zirconyl nitrate hydrate, zirconyl nitrate, zirconyl perchlorate octahydrate, and combinations thereof. 
     
     
       55. A process according to  claim 49  wherein said zirconyl salt comprises zirconyl nitrate hydrate. 
     
     
       56. A process according to  claim 49  wherein said process of preparing said zirconium phosphate further comprises contacting with an aqueous solution. 
     
     
       57. A process according to  claim 49  wherein said process of preparing said zirconium phosphate further comprises contacting with an alcohol selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and combinations thereof. 
     
     
       58. A process according to  claim 49  wherein said process of preparing said zirconium phosphate further comprises pressure drying under a pressure drying condition comprising:
 a temperature in the range of from about 200° C. to about 500° C.,  
 a pressure in the range of from about 14.7 pounds per square inch absolute to about 400 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 10 hours, and  
 further wherein said pressure drying condition comprises an atmosphere selected from the group consisting of nitrogen, argon, and combinations thereof.  
 
     
     
       59. A process according to  claim 49  wherein said process of preparing said zirconium phosphate further comprises drying under a drying condition comprising:
 a temperature in the range of from about 20° C. to about 200° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 200 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 10 hours, and  
 further wherein said drying condition comprises an atmosphere comprising air.  
 
     
     
       60. A process according to  claim 49  wherein said process of preparing said zirconium phosphate further comprises calcining under a calcining condition comprising:
 a temperature in the range of from about 250° C. to about 1000° C.,  
 a pressure in the range of from about 0 pounds per square inch absolute to about 750 pounds per square inch absolute,  
 a time period in the range of from about 0.5 hour to about 30 hours, and  
 further wherein said calcining condition comprises an atmosphere comprising air.  
 
     
     
       61. A process of preparing a high molecular weight hydrocarbon comprising contacting, under reaction conditions, a catalyst composition, comprising zirconium and ruthenium, and a fluid comprising hydrogen and carbon monoxide, wherein said zirconium is present in a zirconium component selected from the group consisting of zirconium oxide, zirconium phosphate, zirconyl phosphate, and combinations thereof wherein said contacting is conducted in the presence of a solvent selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane, and combinations thereof. 
     
     
       62. A process according to  claim 61  wherein said high molecular weight hydrocarbon comprises a molecular weight greater than about 2×10 3  molecular weight units. 
     
     
       63. A process according to  claim 61  wherein said high molecular weight hydrocarbon comprises polymethylene. 
     
     
       64. A process according to  claim 61  wherein a weight ratio of said zirconium to said ruthenium is in the range of from about 0.01:1 to about 5:1. 
     
     
       65. A process according to  claim 61  wherein a mole ratio of said hydrogen to said carbon monoxide is in the range of from about 1:1 to about 5:1. 
     
     
       66. A process according to  claim 61  wherein said reaction conditions comprise:
 a temperature in the range of from about 100° C. to about 500° C.,  
 a pressure in the range of from about 1000 pounds per square inch gauge to about 10,000 pounds per square inch gauge, and  
 a charge rate of said fluid such that the weight hourly space velocity is in the range of from about 0.01 hours −1 to about 1000 hour −1 .  
 
     
     
       67. A process according to  claim 61  wherein a weight ratio of said solvent to catalyst composition is in the range of from about 400:1 to about 20:1. 
     
     
       68. A process according to  claim 61  wherein said process is conducted in a slurry phase reactor.